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• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
  • C08L83/04—Polysiloxanes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/04—Homopolymers or copolymers of ethene
  • C08L23/08—Copolymers of ethene
  • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
  • C08L23/0869—Acids or derivatives thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/12—Polysiloxanes containing silicon bound to hydrogen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
  • C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
  • C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/70—Siloxanes defined by use of the MDTQ nomenclature
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
  • C08K3/016—Flame-proofing or flame-retarding additives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/34—Silicon-containing compounds
  • C08K3/346—Clay
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2201/00—Properties
  • C08L2201/02—Flame or fire retardant/resistant
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2203/00—Applications
  • C08L2203/20—Applications use in electrical or conductive gadgets
  • C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/04—Homopolymers or copolymers of ethene
  • C08L23/06—Polyethene

Definitions

• the present invention relates to a flame retardant polymer composition, more particularly to a flame retardant polymer composition for wires or cables which shows reduced dripping properties while retaining other properties such as hard inflamability, good extrudability or a good balance between flexibility and stiffness. Furthermore, the present invention relates to the use of the flame retardant polymer composition for the production of a flame retardant layer in wires or cables as well as to a wire or cable comprising a flame retardant composition according to the invention.
• Polyolefins are inherently combustible materials. However, in many applications flame resistance is required such as for cables and wires in the Electronics and Electrical industries.
• specific additives such as halogen based chemicals, phosphate based chemicals or inorganic hydroxide/hydrated compounds.
• halogen based chemicals such as halogen based chemicals, phosphate based chemicals or inorganic hydroxide/hydrated compounds.
• phosphate based chemicals such as phosphate based chemicals or inorganic hydroxide/hydrated compounds.
• Each of these additives have their own deficiencies, such as incompatibility with the polyolefin, the need for high loading levels leading to poor mechanical properties and poor processability, the presence or emission of harmful, toxic or otherwise undesirable compounds and high costs.
• EP 0 393 959 provides a flame retardant polymer composition comprising a silicone fluid or gum filler and a non-hydrated/non-hydroxide inorganic filler.
• This composition shows good flame retardant properties due to the formation of a stable char layer on combustion.
• the dripping properties of these materials still need improvement because dripping of inflamed polymer boosts the progression of a fire.
• the present invention is based on the finding that this object can be achieved by a polymer composition which in addition to a polymer comprises a silicone-group containing compound and a nanofiller.
• the present invention provides therefore a reduced dripping flame retardant polymer composition
• a reduced dripping flame retardant polymer composition comprising
• the inventive composition shows very good flame retardant properties combined with reduced dripping properties compared to materials known in the art. Furthermore, the incorporation of components (B), (C) and (D) into polyolefin (A) surprisingly leads to a synergistic effect with regard to the maximum heat release rate which is lower than in compositions different to the invention. Thus, with the inventive composition the danger of flashover due to sudden heat built-up leading to ignition of flammable materials in the vicinity of, for example, a wire comprising the inventive composition is reduced.
• polymer (A) The choice and the composition of polymer (A) varies, depending on whether the inventive composition is used as a layer for wires or cables and depending on for what purpose the layer is used.
• polymer (A) may also comprise a mixture of different polymers.
• Suitable polymers for forming component (A) include polyolefins, polyesters, polyethers and polyurethanes.
• Elastomeric polymers may also be used such as, for example, ethylene/propylene rubber (EPR), ethylene/propylene-diene monomer rubbers (EPDN), thermoplastic elastomer rubber (TPE) and acrylonitrile butadiene rubber (NBR).
• Silane-crosslinkable polymers may also be used, i.e. polymers prepared using unsaturated silane monomers having hydrolisable groups capable of crosslinking by hydrolysis and condensation to form silanol groups in the presence of water and, optionally, a silanol condensation catalyst.
• component (A) is essentially formed by olefin, preferably ethylene, homo- or copolymers.
• olefin preferably ethylene, homo- or copolymers.
• ethylene preferably ethylene, homo- or copolymers.
• ethylene preferably ethylene, homo- or copolymers.
• Suitable homopolymers and copolymers of ethylene include low density polyethylene, linear low, medium or high density polyethylene and very low density polyethylene.
• Suitable ethylene copolymers include such with of C 3 - to C 20 -alpha-olefins, C 1 - to C 6 - alkyl acrylates, C 1 - to C 6 - alkyl methacrylates, acrylic acids, methacrylic acids and vinyl acetates.
• Preferred examples for the alkyl alpha-olefins are propylene, 1-butene, 4-methyl-1-pentene, 1-hexene and 1-octene.
• composition component (A) comprises an olefin copolymer, preferably a polar olefin copolymer.
• Polar groups are defined to be functional groups which comprise at least one element other that carbon and hydrogen.
• the polar copolymer is an olefin/acrylate, preferably ethylene/acrylate, and/or olefin/acetate, preferably ethylene/acetate, copolymer.
• the polar copolymer comprises a copolymer of ethylene with one or more comonomers selected from C 1 - to C 6 -alkyl acrylates, C 1 - to C 6 -alkyl metacrylates, acrylic acids, metacrylic acids and vinyl acetate.
• the copolymer may also contain ionomeric structures (like in e.g. DuPont's Surlyn types).
• the polar polymer comprises a copolymer of ethylene with C 1 - to C 4 -alkyl, such as methyl, ethyl, propyl or butyl, acrylates or vinylacetate.
• the copolymers may also contain further monomers.
• the copolymers can contain up to 10% by weight of an olefin such as propylene.
• the polar copolymer may be produced by copolymerisation of the polymer, e.g. olefin, monomers with polar comonomers but may also be a grafted polymer, e.g. a polyolefin in which one or more of the comonomers is grafted onto the polymer backbone, as for example acrylic acid-grafted polyethylene.
• the polar polymer makes up an amount of 30 parts by weight (pbw) or more, more preferred of 50 pbw or more, and still more preferred of 70 pbw or more, per 100 pbw of component (A).
• the inventive reduced dripping flame retardant composition further comprises a silicone-group containing compound (B).
• component (B) is a silicone fluid or a gum, or an olefin, preferably ethylene, copolymer comprising at least one silicone-group containing comonomer, or a mixture of any of these compounds.
• said comonomer is a vinylpolysiloxane, as e.g. a vinyl unsaturated polybishydrocarbylsiloxane.
• Silicone fluids and gums suitable for use in the present inventions are known and include for example organopolysiloxane polymers comprising chemically combined siloxy units selected from the group consisting of R 3 SiO 0.5 , R 2 SiO, R 1 SiO 1.5 , R 1 R 2 SiO 0.5 , RR 1 SiO, R 1 2 SiO, RSiO 1.5 and SiO 2 units and mixtures thereof in which each R represents independently a saturated or unsaturated monovalent hydrocarbon radical and each R 1 represents a radical such as R or a radical selected from the group consisting of hydrogen, hydroxyl, alkoxy, aryl, vinyl or allyl radicals.
• organopolysiloxane polymers comprising chemically combined siloxy units selected from the group consisting of R 3 SiO 0.5 , R 2 SiO, R 1 SiO 1.5 , R 1 R 2 SiO 0.5 , RR 1 SiO, R 1 2 SiO, RSiO 1.5 and SiO 2 units and mixtures thereof in which each
• the organopolysiloxane preferably has a viscosity of approximately 600 to 300 x 10 5 centipoise at 25° C.
• the silicone fluid or gum can contain fumed silica fillers of the type commonly used to stiffen silicone rubbers, e.g. up to 50% by weight.
• component (B) is polydimethylsiloxane, preferably having a viscosity of preferably approximately 20 x 10 6 centipoise at 25 °C, and/or a copolymer of ethylene and vinyl polydimethylsiloxane. These components (B) are preferred due to commercial availability.
• copolymer as used herein is meant to include copolymers produced by copolymerization or by grafting of monomers onto a polymer backbone.
• Component (C) i.e. the inorganic filler material suitable for use in the inventive composition, comprises all filler materials as known in the art.
• Component (C) may also comprise a mixture of any such filler materials. Examples for such filler materials are oxides, hydroxides and carbonates of aluminium, magnesium, calcium and/or barium.
• component (C) is an inorganic compound of a metal of groups 1 to 13, more preferred groups 1 to 3, still more preferred groups 1 and 2 and most preferred group 2, of the Periodic Table of Elements.
• inorganic filler component (C) comprises a compound which is neither a hydroxide, nor a hydrated compound, more preferred comprises a compound selected from carbonates, oxides and sulphates, and most preferred comprises a carbonate.
• Preferred examples of such compounds are calcium carbonate, magnesium oxide and huntite Mg 3 Ca(CO 3 ) 4 , with a particular preferred example being calcium carbonate.
• inorganic filler (C) preferably is not a hydroxide, it may contain small amounts of hydroxide typically less than 5% by weight of the filler, preferably less than 3% by weight. For example there may be small amounts of magnesium hydroxide in magnesium oxide.
• filler (C) is not a hydrated compound, it may contain small amounts of water, usually less than 3% by weight of the filler, preferably less than 1% by weight. However, it is most preferred that component (C) is completely free of hydroxide and/or water.
• component (C) of the inventive flame retardant polymer composition comprises 50 wt% or more of calcium carbonate and further preferred is substantially made up completely of calcium carbonate.
• the inorganic filler may comprise a filler which has been surface-treated with an organosilane, a polymer, a carboxylic acid or salt etc. to aid processing and provide better dispersion of the filler in the organic polymer.
• Such coatings usually do not make up more than 3 wt.% of the filler.
• compositions according to the present invention contain less than 3 wt.% of organo-metallic salt or polymer coatings.
• the aspect ratio of the inorganic filler particles i.e. the ratio between the widest and shortest dimension of the particles is 5 or less.
• the average particle size of inorganic filler (C) is 0.3 micrometer or more, more preferred 0.5 micrometer or more and still more preferred 1.0 micrometer or more.
• the inventive composition comprises a nanofiller (D).
• nanofiller refers to substances with the ability to disperse in the matrix polymer in such a way that structures in the nanoscale dimension (1 to 700 nm) are observed.
• the particles of the nanofiller are dispersed in the polymer matrix so that the maximum thickness in at least one dimension is 10 nm or less, more preferably 8 nm or less.
• Nanocomposites Polymer matrices in which a nanofiller is dispersed as described above are usually designated as "nanocomposites".
• this term designates a multiphase material where one phase, i.e. the nanofiller, is dispersed in one or more other phases at a nanometer level in such a way that structures in the nanoscale dimension (1 to 700 nm) are observed.
• a nanocomposite material appears homogeneous on a microscopic scale.
• the inventive polymer composition can also be designated as a nanocomposite.
• nanofillers all particulate or layered materials may be used as long as they have the ability to disperse in the matrix polymer to form a nanocomposite.
• the nanofiller may be an inorganic material such as a clay-based layered material, a conventional sub-micron filler such as talc, calcium carbonate and mica with suitable small particle dimensions, preferably with an average particle size of below 10 nm (usually obtained by grinding), a nanovisker such as SiC, silica and special compounds such as carbon nanotubes.
• a conventional sub-micron filler such as talc, calcium carbonate and mica with suitable small particle dimensions, preferably with an average particle size of below 10 nm (usually obtained by grinding)
• a nanovisker such as SiC, silica and special compounds such as carbon nanotubes.
• nanofiller component (D) may also comprise a mixture of different nanofillers such as a mixture of a clay-based nanofiller and talc.
• the dispersion of the above mentioned layered materials used as nanofillers in the polymer matrix is caused by the delamination or exfoliation of the layers of these materials.
• nanofiller (D) is a clay-based layered inorganic, preferably silicate, material or material mixture.
• Useful such clay materials include natural, synthetic and modified phyllosilicates.
• Natural clays include smectite clays, such as montmorillonite, hectorite, mica, vermiculite, bentonite.
• Synthetic clays include synthetic mica, synthetic saponite, synthetic hectorite.
• Modified clays include fluoronated montmorillonite and fluoronated mica.
• the particles of clay-based layered inorganic materials have an aspect ratio at 10 or more.
• Layered silicates may be made organophilic before being dispersed in the polymer matrix by chemical modification such as by cation exchange treatment using alkyl ammonium or phosphonium cation complexes. Such cation complexes intercalate between the clay layers.
• a smectite-type clay which comprises montmorillonites, beidellites, nontronites, saponites as well as hectonites.
• the most preferred smectite-type clay is montmorillonite.
• the amount of all components (B), (C) and (D) together does not exceed 75 wt% in the total composition. Further preferred, the amount of all components (B), (C) and (D) together is in the range of 10 to 75 wt%, more preferably 30 to 70 wt% and most preferably 35 to 50 wt%.
• the amount of both components (C) and (D) together does not exceed 50 wt%, more preferred 40 wt% in the total composition.
• silicone-group containing compound (B) is present in the composition in an amount of 0.5 to 40 %, more preferred 0.5 to 10 % and still more preferred 1 to 5 % by weight of the total composition.
• inorganic filler (C) is present in in the composition an amount of 5 to 70 wt%, more preferably 15 to 60 wt% and most preferably 20 to 40 wt%.
• nanofiller (D) is present in an amount of 0.5 to 20 wt%, more preferably 1 to 10 wt% and most preferably 2 to 7 wt% in the total composition.
• the nanofiller (D) is present in amount of 2 to 20 wt%, more preferably 5 to 17 wt% and most preferably 5 to 15 wt% of the total of fillers (C) and (D).
• the composition may also comprise a metal stearate, preferably magnesium stearate. Further preferred, a stearate is added to the composition in a small amount, preferably of 5 wt. % or less, more preferably of 2 wt. % or less.
• the composition comprises an ethylene butyl acrylate copolymer, polydimethylsiloxane, calcium carbonate and alkyl quarternary ammonium montmorillonite. It is preferred that in this composition the ethylene butyl acrylate copolymer ranges from 50 to 60 wt% in the total composition, polydimethylsiloxane ranges from 1 to 5 wt% in the total composition, calcium carbonate ranges from 28 to 33 wt% in the total composition and alkyl quarternary ammonium montmorillonite ranges from 3 to 5 wt% in the total composition.
• the time to drip after ignition is measured as defined in the Example section below.
• the rate of maximum and average heat release rate (HRR max) (kW/m 2 ) was measured using a cone calorimeter (35 kW/m 2 , 3 mm plaques) according to ISO 5660-1V.
• Tensile modulus is the ratio of stress to strain within the elastic region of the stress-strain curve, prior to the yield point.
• the tensile modulus is usually measured at very low strains where the proportionality of stress to strain is at its maximum.
• the shape of the stress-strain curves gives is indicative of the material's behaviour.
• a hard, brittle material shows a large initial slope and fails with little strain.
• a soft and tough material exhibits a very small initial slope, but strain hardens and withstands larger strains before failure.
• Tensile modulus and strength were measured as indicated in the Example section below.
• composition according to the present invention may contain additional ingredients, such as for example antioxidants and or UV stabilizers, in small amounts.
• additional ingredients such as for example antioxidants and or UV stabilizers, in small amounts.
• other mineral fillers such as glass fibres may be part of the composition.
• compositions according to the present invention may be cross-linkable. It is well known to cross-link thermoplastic polymer compositions using cross-linking agents such as organic peroxides and thus the compositions according to the present invention may contain a cross-linking agent in a conventional amount. Silane cross-linkable polymers may contain a silanol condensation catalyst.
• the reduced dripping flame retardant polymer composition may be prepared by
• the nanofiller is preferably premixed with the polymer prior to compounding.
• a conventional compounding or blending apparatus e.g. a Banbury mixer, a 2-roll rubber mill, Buss-co-kneader or a twin screw extruder may be used.
• the composition will be prepared by blending them together at a temperature which is sufficiently high to soften and plasticise the polymer, typically a temperature in the range of 120 to 200 °C.
• the reduced dripping flame retardant composition according to the present invention can be used in many and diverse applications and products.
• the composition can for example be moulded, extruded or otherwise formed into mouldings, sheets, webbings and fibres.
• a particularly preferred use of the flame retardant composition according to the present invention is for the manufacture of wires or cables.
• the composition can be extruded about a wire or cable to form an insulating or jacketing layer or can be used as a blending compound.
• Flame retardant polymer compositions according to the invention and for comparative purpose were produced by compounding together the components in a Buss-co-kneader at a temperature of 150°C.
• the "Screw" speed was 85 rpm.
• compositions were compounded as indicated above with amounts given in weight% of the components as indicated in Table 1.
• the melt flow rate of the composition was measured in accordance with ISO 1133 at 190°C and a weight of 2.16 kg.
• the tensile strength and the tensile modulus were measured in accordance with ISO 527.
• the time to drip of the compositions was measured in the following way:

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• 2003
  • 2003-08-27 EP EP03019363A patent/EP1512718A1/de not_active Withdrawn
• 2004
  • 2004-08-25 US US10/569,938 patent/US20080194749A1/en not_active Abandoned
  • 2004-08-25 WO PCT/EP2004/009492 patent/WO2005021641A1/en active Application Filing
  • 2004-08-25 CN CNA2004800246523A patent/CN1842571A/zh active Pending
  • 2004-08-25 EA EA200600464A patent/EA008099B1/ru not_active IP Right Cessation

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